Making alkylene chlorohydrins and aliphatic esters conjointly



Patented Jan. 8, 19 35 I 7 l a I MAKING ALKYLENE CHLOROHYDRINS AND ALIPHATIC ESTERS'CONJOINTLY I Edgar C. Britton, Gerald H. cole mamand Garnett V.-More, Midland, Mich., assig'nors to The Dow Chemical Company, Midland, Mich., a corporationof Michigan I I "N0 Drawing.= Application July 17, 1933, Serial No. 680,784 A y 5Claims. (Cl. 260- 1 06') The invention regardsaprocess for making an hydrogen chloride. Themixture was then placed alkylene chlorohydrinand an ester of a satuin a copper-linedrocker bomb and maintained rated aliphatic mono-carboxylic acid by reacting at-a temperatureof 150 C. forthree hours. The an alkylene glycol diester of a saturated aliphatic reaction mixture was then removed from the 5 mono-carboxylic acid with hydrogen chloride and bomb and fractionally distilled. The approxi- 5 a primary or secondary aliphatic alcohol or mate yields obtained were: propylene chloroaralkyl alcohol. The following description sets hydrin80 per cent of theoretical; and normalforth in detail several approved modes of carbutyl acetate81 per cent of theoretical.

rying out the invention, such disclosed modes Examme 4 10 illustrating, however, but several of various ways 10 in which the principle of the invention may be A mixture consisting of 1 mol of ethylene glycol used. dipropionate, 2.5 mols of normal-.propyl alcohol,

The following equation illustrates the reaction and 1 mol of hydrogen chloride was maintained involved in our invention:- at refluxing temperature for 5 hours. The reacwherein R represents either hydrogen or an alkyl tion mixture was then fractionally distilled to obgroup; R represents an alkyl group; and R tain an approximate yield of 75 per cent of theo- 0 represents either a primary or secondary alkyl retical o-f normal-propyl' propionate and 72'per I group, or an aralkyl group. cent of ethylene chlorohydrin.

To show the results obtained by practicing our We have used the aralkyl alcohols, such as invention, the following examples are given: benzyl alcohol and phenyl; ethyl alcohol in car- 7 Example 1 rying out the foregoingprocess. We have been 25 unable to use a tertiary aliphatic alcohol due A mixture consisting of 9.5 mols of ethylene to decomposition thereof under reaction condiglycol diacetate and mols of 96 per cent ethyl tions. alcohol was saturated with 9.7 mols of gaseous It is to be noted that the boiling points of.

30 hydrogen chloride. This mixture was then certain of the chlorohydrins and esters are so 30 I placed in a copper-lined bomb, agitated, and close together that mixtures thereof are very difmaintained at a temperature of l25-135 C. for ficult to separate, and, unless it is desired to utitwo hours. The reaction mixture was then relize the reaction mixture as a solvent without moved from the bomb and fractionally distilled. separating the various components thereof, care. The approximate yields obtained were: ethylene must be exercised in selecting an alcohol which 35 chlorohydrin'78 per cent of theoretical; and will yield an ester with a boiling point somewhat ethyl acetate89 per cent of theoretical. removed from that of the chlorohydrin conjoint- Emample 2 ly obtained. The reaction is preferably run in an excess of alcohol, and the resulting reaction 40 A mixture consisting o 10 mols of ethylene mixture containing chlorohydrin, ester, and ex- 40 glycol diacetate and 25 mols of secondary butyl cess alcohol is an excellent lacquer solvent. alcohol was saturated with 10 mols of gaseous Inconclusion, our process provides an advanhydrogen chloride. This mixture was heated for tageous method for making a substantially antwo hours at a temperature of about 150 C. in hydrous alkylene chlorohydrin and an ester of a pp -lined bomb. The reaction mixture was a saturated aliphatic mono-carboxylic acid con- 45 removed from the bomb and fractlonally disjointly, tilled, the yields obtained being approximately: Other modes of applying the principle of our ethylene chlorohydrin70 per cent of theoretiinvention may be employed instead of those excal; and. secondary butyl acetate82 per cent plained, change being made as regards theprocof theoretical. ess herein disclosed, provided thestep or steps 50 Example 3 stated by any of the following claims or the equivalent of such stated step or steps be em- A mixture consisting of 4.94 mols of propylene ployed. glycol diacetate and 12.35 mols of normal-butyl We therefore particularly point out and dis- 5 alcohol was saturated with 5.15 mols of gaseous tinctly claim as our invention:-

r 1'. The 'method which comprises reacting" an alkylene glycol diester of a saturated aliphatic mono-carboxylic acid with hydrogen chloride and an alcohol selected from the class consisting of primary and secondary alkyl and aralkyl alcohols to forman alkylene chlorohydrin andzan ester of the alcohol and said aliphatic mono-carboxylic acidQ j c 2. The method which comprises subjecting a mixture of an alkylene glycol'diester-of :a-.-saturated aliphatic mono-carboxylic acid .hydrogen' chloride, and an alcohol selected from the class consisting of primary and "secondary -alkylxand aralkyl alcohols to a temperature above-iabout'fi 50 C. whereby an alkylene chlorohydrin and an ester of the alcohol and said aliphatic mono- -carboxylic acid are formed.

3. The method which comprises reacting'an' alkylene glycol diester. of a saturated aliphatic mono-carboxylic acid with hydrogen chloride and an. alcohol: selected xifiiommthe-class. consisting of primary :and secondary alkyl and .aralkyl alcohols at. superatmospheric pressure eand at a temperaformed.

5; A'processiforimaking ethylene chlorohydrin and ethylacetate. which comprises admixing ethylene glycol diacetate with hydrogen chloride and iethylalcohoh heating the mixture under pressure at a temperature of 125-135, C., and recoveringethylene chlorohydrin and ethyl acetate from the reaction mixture.

GARNETIYY; MCDORE: 

